Molecular Speciation of Isopolyoxomolybdates and Isopolyoxotungstates with Silicic Acid in Aqueous Solution Using ESI-MS
Molecular Speciation of Isopolyoxomolybdates and Isopolyoxotungstates with Silicic Acid in Aqueous Solution Using ESI-MS
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使用 ESI-MS 对水溶液中异多钼氧酸盐和异多钨酸盐与硅酸进行分子形态分析
DOI：
10.1007/s10953-023-01255-6
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发表时间：
2023
影响因子：
1.2
通讯作者：
Tanaka Miho
中科院分区：
文献类型：
--
作者：
Osuka Yuri;Ii Kyota;Tsuchiya Kotaro;Nemoto Masao;Sahoo Yu Vin;Takahashi Kazuya;Tanaka Miho
利用电喷雾质谱技术对纯水中钨酸盐和钨酸盐物种进行表征的报道很少。六元环阴离子在中性溶液中不稳定，但在酸性溶液中存在。单钼酸盐阴离子在纯水溶液中以[HMoO 4]−的形式稳定。钨酸盐在酸性溶液中以[WO 4]2−和[HWO 4]−形式存在。在低pH下，[Mo 4 O 13]2-、[HMo 4 O 13]-和[HW 3 O 10]-是观察到的主要分子种类。在高pH值下，通过质谱仪检测水解的[HMoO 4]−和[HWO 4]−。当向Na 2SO 4溶液中加入Na 2SO 4酸时，四聚Na 2SO 4阴离子形成[SiMo 12 O 40]4-和[HSiMo 12 O 40]3-。此外，通过ESI质谱法在上清液中检测到单体、三聚体、六聚体、七聚体、十一聚体和十二聚体多钼酸盐。当将钨酸加入到钨酸盐溶液中时，检测到由三聚钨酸盐阴离子组成的[HSiW 12 O 40]3−。此外，两个五聚体的多钨酸盐以及四聚体，六聚体和七聚体的多钨酸盐存在于上清液溶液中，而没有检测到单体或二聚体。
There have been few reports on the characterization of molybdate and tungstate species in pure water using ESI–MS. Hexameric molybdate anions were reported to be unstable in neutral solution, but to exist in acidic solutions. The monomolybdate anion was found to be stable in pure aqueous solution in the form of [HMoO4]−. Monomeric tungstate was observed as [WO4]2−and [HWO4]−in acidic solution. At low pH, [Mo4O13]2−, [HMo4O13]−and [HW3O10]−were the main molecular species observed. At high pH, hydrolyzed [HMoO4]−and [HWO4]−were detected by mass spectometer. When silicic acid was added to the molybdate solution, [SiMo12O40]4−and [HSiMo12O40]3−were formed from the tetrameric molybdate anion. In addition, monomeric, trimeric, hexameric, heptameric, undecameric and dodecameric polyoxomolybdates were detected in the supernatant solution by ESI mass spectrometry. When silicic acid was added to a tungstate solution, [HSiW12O40]3−, composed of the trimeric tungstate anion was detected. In addition, two pentameric polyoxotungstates as well as tetrameric, hexameric and heptameric polyoxotungstates were present in the supernatant solution, while no monomer or dimer was detected.